Water-soluble salts of amidines and derivatives thereof



I Patented Feb. 14, 1939 'UNITED' STATES PATENT orrica I WATER-SOLUBLE SALTS F AM'IDINES AND DERIVATIVES THEREOF Alfred Eckelmann and Ernst Koch, Frankforton-the-Main-Hochst,- Germany, assignors to General Aniline Works, Inc., New a corporation of Delaware York, N. Y.,

No Drawing. Application November 2, 1934, Se-

. rial No. 751,253.

7 Claims.

The present invention relates to water-soluble salts of amldines and derivatives thereof and to fibrous materials treated with these products.

In Germany November 9,

with acetamidine hydrochloride of the following constitution:

pregnatlons which are fast to creasing it is ad- NH vantageous to add bufl'ering substances such as, Hm hexamethylenetetramine in order to protect the I have fiber from being deteriorated. In other cases the stability to washing of dressings or impregnations NH We have found that fibrous materials, such as Caro H01 5 textiles, paper or pasteboard may be advanta- 5 geously treated with the hitherto unknown water- N H1 soluble salts of amidines or derivatives thereof which are obtainable by treating mixtures of at furthermore the amidme hydrochloride of tech least 2 imidoether salts or imidothioether salts, steam acid the diethylamldme hydmchmat least one of which contains more than 6 ride from coco-nut oil fattyacid, the amidine hym hon atoms, with compounds of fonowiug gem drochlonde obtained from the nitrile of a paraferal formula: fin carboxylic acid which has been prepared by R oxidation of paraflin with air, the amidine hy- H drochloride prepared from imidoethylether byu drochloride of technical stearic acid by reaction w R: with ethylene diamine, the amidine formate of palm nut oil fatty acid, the amldine oxalate of g gfigi z g z x g'z g gggigg gggfigfig i an coco-nut oil fatty acid, the product prepared by AS m1 tures or imldoether salts there be entirely meithfyltstmgithe tarriidine obtained from l t l i mentioned, for instance, the lmldomethylether fi fli i-5,225 2 5 ebesides a good dis hydrochloride of technical stearic acid, the imidopersive and l if i power an excellent action ethylether hydrochloride of entirely brominated as Softening agent By treating fib material 2x2 122 3 21 1; 3:1 3; i sh i igif i lm igg gfi 122 such as colored or uncolored textiles, paper or 25 hydrochloride of coco-nut oil fatty acid, tile im- $3: EZ SQ gE $EPZZ K igggf g gg g ifif 25 iig g gggfig gl ;31 53253233 52? priie'gnation effetfitihsinfcizge the substances improve e soft feel 0 e rs. According to their acid, the imidoethylethel hydrmhmride tech construction, the products are suitable for being nical resin acid, the imidophenylether hydrochloused, fo instance, as washing vwetting, levelling w ride of coco-nut Oil acid, the lmidoethylthioemuls fy ng or dispersing a gents as resists for ether hydrochloride of technical steam the rendering viscose artificial tissues fast to creasing, ig ggg a gfif hydrochloride of technical naphior delustring artificial silk and for after-treatingcolored materials.

35 AS Products of the general frmu1a The solubility and stability of the solutions of 3% certain of the salts'of these amiclines may be enhanced by using simultaneously during the preparation or application of the solutions emulsify- R: ing or dispersing, agents or protective colloids. F As such assistants there may be mentioned, for 3 1 2 gi h fifi gig' g gg if instance, the salts of urethanes carrying sulfo or g dibui ethylenedgmmmmne g carbonyl groups, fatty alcohol sulfonates, waterth m y diethnolamme hen i d1 soluble oxethylated fatty alcohols, oxethylated 9 g i e i fatty amines, oxethylated esters or amides of a? ermor urea m or higher fattyacids, carbohydrates, oxethylated or m i :teps-oluble salts of ammmes there may Olther watergsolubleblalbuhminous products and be mentioned, for instance: mixtures of salts of EJ5 11; 3 21 5 9 the 13 33 32 subiiili fiiiiiifiiiliitiiifiiitiitifiifihlfii Insome de o t following constitution: of dressings which are fast to washing and im- 50 may be improved by working in the presence of inorganic or organic ammonium salts.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight unless otherwise stated:

1. 100 parts of imidoethylether hydrochloride, obtainable from coco-nut oil fatty acid nitrile, are dissolved in absolute alcohol. Thereupon, an amount of ammonia gas is added which exceeds the calculated quantity by a little, and the whole is slowly warmed to 50 C., whereupon the ammonium chloride which has first precipitated, disappears for the most part. After filtration, the alcohol is removed by distilling it off in vacuo, and the amidine hydrochloride is washed out with ether. The yield amounts to 87 parts; the product obtained is easily soluble in water.

This product is suitable for being used as wetting agent in the textile industry.

2. 32 parts of anhydrous methyl alcohol are added to 195 parts of nitrile. mixture prepared from palm nut oil fatty acid (boiling at 100 C. to 125 C. under a. pressure of mercury of 2 mm., corresponding with about 68% of laurylnitrile and about 32% of myristilnitrile) and, at about 10 C., 38 parts of hydrogenchloride are introduced into the mixture. After a prolonged standing in the cold the reaction mass solidifies. By treating it with ethylene diamine in a methylalcoholic solution, it is converted into the corresponding amidine.

By treating mixed fabrics consisting of viscose artificial silk and natural silk with a formaldehyde solution of 20% strength which contains per liter 20 grs. of the above described product, the goods obtained, after squeezing and drying at 80 C., to 90 C., are fast to creasing and have an agreeable soft feel.

3. 245 parts of nitrile of a .carboxylic acid which is obtainable by oxidation of parafiin by means of air, are mixed with 64 parts of methyl alcohol. '76 parts of hydrogen chloride are introduced into this mixture at C. to C., while stirring. Stirring is continued and the product then is allowed to stand for several hours. Thereupon, the whole is mixed with 200 parts of methyl alcohol and 210 parts of methylalcoholic ammonia solution; the whole is then heated to 50 C. Thereupon, the methanol is distilled ofl under a feebly' reduced pressure and the residue is taken up in ether. The solution obtained is cooled to about 0 C., filtered with suction and the solid matter is washed with ether. The pure amidine hydrochloride is thus obtained. By using this product for dyeing cotton tissue in a weight of 2% of that of the tissue to'be dyed,

. there is obtained a very good levelling effect.

-amidine hydrochloride which contains 4% of the weight of the goods to be dyed, the material shows, when dyed with basic dyestufi's, a good resist effect, 1. e. the cotton does not absorb the dyestufi.

5. 665 parts of imidomethylether hydrochloride, obtainable from the nitrile of technical stearicacidareintroduced into lmpartsot methyl alcohol and, simultaneously, 162 parts of ethylene diamine of 74% strength are dropped in. The whole is boiled for 3 hours in a reflux apparatus. The whole is filtered by suction, the alcohol is distilled oflf and the amidino hydrochloride is washed out with ether. By treating cotton which has been dyed with a substantive dyestuil', with a solution of 0.1% of this product the dyeing becomes very fast to the action of water, perspiration and acids. Also the fastness to washing is considerably enhanced by such an after-treatment.

6. 150 parts of imidoethylether hydrochloride, obtainable from palm nut oil fatty acid nitrile, are dissolved in absolute alcohol. While stirring, about the calculated amount of ammonia gas is introduced and the whole is then warmed at about 40 C. to 50 C. After filtration, the alcohol is removed by distillation and the amidine hydrochloride is washed out with ether.

By treating crude viscose artificial silk which still contains sulfur for 1 hour at 90 C. with solution of 2% of this product, there is obtained a very desulfurized artificial silk which possesses an excellently soft feel.

We claim:

1. Water-soluble mixtures of acid addition salts of amidines, said mixtures being obtainable by causing a mixture of acid addition salts of imido-ethers obtained by converting technical stearic acid into the corresponding acid addition salts of imido-ethers, to react with ethylenediamine.

2. Water-soluble mixtures of acid addition salts of amidines, said mixtures being obtainable by causing a mixture of acid addition salts of imido-ethers obtained by converting technical stearic acid into the corresponding acid addition salts of imido-ethers, to react with diethylamine.

3. Water-soluble mixtures of acid addition salts of amidines, said mixtures being obtainable by causing a mixture of acid addition salts of imido-ethers obtained by converting paraflln carboxylic acid into the corresponding acid addition salts of its imido-ether, to react with ammonia.

.4. Mixtures of acid addition salts of amidines containing at least one addition salt of the formula wherein R means an aliphatic hydrocarbon radical of at least 11 carbon atoms, R: and R: stand for a memberof the group consisting of H and aliphatic hydrocarbon radicals, Ac means an acid, and at least one addition salt of the formula wherein 1?. means an aliphatic hydrocarbon radical, R: and R: stand for a member of the group consisting of H and aliphatic hydrocarbon radicala. Ac means an acid.

5. Mixtures of acid addition salts of amidines an acid addition sait of the formula containing an addition acid salt of the formula an addition salt of the formula and an acid addition salt of the formula olin-0' -Ac Ell N\ Gully-C CnHr-C om in which formulae R2 and R3 stand for a member of the group consisting of H and aliphatic hy drocarbon radicals, Ac stands for an acid.

7. Mixtures of acid addition salts of amidines wherein It means a member of-the group consisting of aliphatic hydrocarbon radicals of at least 11 carbon atoms and cycloaiinhatic hydrocarbon radicals, R: and R: stand for a member of the group consisting of E and aiitic hydrocarbon radicals, Ac means an acid, and at least one addition salt of the formula R-O ac Rn wherein R means a member of the group consistin: of aliphatic hydrocarbon radicals, R2 and R; stand for a member of the group consisting of H and aliphatic hydrocarbon radicals. Ac means an acid.

ALFRED E.

ERNST KOCH. 

